Search results for "Stereoselectivity"
showing 10 items of 325 documents
Total Synthesis of (-)-C/D-cis-Dehydro-3-O-methyl-estradiols
2015
A convergent synthesis of (–)-dehydro-3-O-methyl-C/D-cis-estradiol started from stereochemically defined substituted optically active 3-(2-arylethyl)-γ-butyrolactones. Regioselective bromination of the anisyl moiety, reductive ring opening of the iodolactone, and protecting-group changes led to a Weinreb amide. This then underwent an intramolecular Grignard reaction closing the B-ring to give a tetralone with defined configuration. Introduction of C-11 through an allyl Grignard addition and subsequent ring-closing metathesis gave a tetrahydro phenanthrene derivative. Oxidation of the side-chain alcohol resulted in the key aldehyde group, and a final samarium-diiodide-mediated reductive D-ri…
Reductive transformations - 11. stereoselective cycloannelation and bridging of the cyclooctatetraene dianionMakromol. Chem., Rapid. Commun. 1988, 9,…
1988
Abstract Bifunctional electrophiles with C4-, C6-, and C8-chains are reacted with the cyclooctatetraene dianion to selectively give novel cycloannelation and bridging products which possess a surprising stereochemistry and are useful starting compounds for further syntheses.
Total synthesis of the monoterpenes (−)-mintlactone and (+)-isomintlactone
1992
Abstract The first total stereodirected synthesis of the monoterpenes (−)-mintlactone and (+)-isomintlactone from the same chiral starting product is described. A stereoselective, radical-mediated ring closure was the key step in both syntheses.
Total synthesis of (−)-mintlactone
1991
Abstract The first total, stereodirected synthesis of (—)-mintlactone is described. A stereoselective, radical-mediated ring closure was the key step in the synthesis.
A molecular electron density theory study of the mechanism, chemo- and stereoselectivity of the epoxidation reaction of R -carvone with peracetic acid
2019
The epoxidation reaction of R-carvone 8 with peracetic acid 9 has been studied within the molecular electron density theory at the B3LYP/6-311(d,p) computational level. The chemo- and stereoisomeric reaction paths involving the two C–C double bonds of R-carvone 8 have been studied. DFT calculations account for the high chemoselectivity involving the C–C double bond of the isopropenyl group and the low diastereoselectivity, in complete agreement with the experimental outcomes. The Baeyer–Villiger reaction involving the carbonyl group of R-carvone 8 has also been analysed. A bonding evolution theory analysis of the epoxidation reaction shows the complexity of the bonding cha…
Stereoselective Synthesis and Structural Correction of the Naturally Occurring Lactone Stagonolide G
2010
A convergent synthesis of the structure proposed for the naturally occurring lactone stagonolide G is described. All three stereocenters were created with the aid of asymmetric Brown allylations. The lactone ring was built by means of a ring-closing metathesis (RCM). The synthetic and the natural compound differed in their spectral properties. A new structure is now proposed for stagonolide G and demonstrated by means of a chemical transformation.
Counterion's Effect on the Catalytic Activity of Zn-Prolinamide Complexes in Aldol Condensations
2012
The catalytic activity of complexes involving organic ligands and Lewis acids can be modulated by changing any of their components. In this work we have studied the influence on the stereoselectivity and catalytic activity exerted by the counterion of zinc salts employed as cocatalysts of L-prolinamide in aldol condensations. The structures of the complexes have been determined both in solution and in the solid state.
ChemInform Abstract: β-Branched α-Halo Carboxylic Acid Derivatives via Stereoselective 1,4-Addition of Dialkylaluminum Chlorides to α,. beta.-Unsatur…
2010
Stereoselective Synthesis of Fluorine-Containing β-Amino Acids
2005
ChemInform Abstract: New Strategy for the Stereoselective Synthesis of Fluorinated β-Amino Acids.
2010
Racemic and chiral nonracemic α-substituted and α-unsubstituted β-fluoroalkyl β-amino acid derivatives 6 and 9 have been synthesized in two steps starting from fluorinated imidoyl chlorides 1 and ester enolates. This approach is based on the chemical reduction of previously obtained γ-fluorinated β-enamino esters 4 by using ZnI2/NaBH4 in a nonchelated aprotic medium (dry CH2Cl2) as the reducing agent. A metal-chelated six-membered model has been suggested to explain the stereochemical outcome of the reduction reaction. The process takes place with high yields and with moderate to good diastereoselectivity. The best results related to diastereoselective reduction of chiral β-enamino esters 4…